Synthesis and characterization of some heterocyclic analogues of N,N′-perarylated phenylene-1,4-diamines and benzidines as a new class of hole transport materials

Article abstract of DOI:10.1055/s-2002-32531

Starting from N,N-diarylsubstituted thioureas 20 and thioacetamides 21 a series of heterocyclic analogous of N,N′-perarylated phenylene-1,4-diamines and benzidines was obtained. These compounds represent, as studied by DSC measurements, a new class of hole transporting materials with high thermal stability and high tendency to form stable amorphous states. Moreover, some of the new compounds are, as measured by cyclic voltammetry, easily reversibly oxidized indicating the formation of persistent radical ions. Such compounds, which are, in general, completely substituted by aryl groups at their heterocyclic moieties, have been successfully used as hole-transport materials in OLEDs.

Full text of DOI:10.1055/s-2002-32531

1268
PAPER
Synthesis and Characterization of Some Heterocyclic Analogues of
N,N -Perarylated Phenylene-1,4-diamines and Benzidines as a New Class
of Hole Transport Materials
H
eterocyc
o
lic Analogue
e
s
a
s
a
N
ew
r
Class of
g
H
ole
T
ransport
MS
aterials chumann,*a Andreas Kanitz,*a Horst Hartmannb
a
SIEMENS AG Erlangen, Paul-Gossen-Str., 91050 Erlangen, Germany
b
University of Applied Sciences, Geusaer Str., 06217 Merseburg, Germany
Fax +49(3461)462192; E-mail: Horst.Hartmann@cui.fh-merseburg.de
Received 5 March 2002
thyl, were used. Usually, these moieties were introduced
in the core of the molecule during synthesis, which usual-
ly requires catalysis by heavy metals. Thus, the N,N -per-
arylated 1,4-phenylene-1,4-diamines 9 and benzidines 10
Abstract: Starting from N,N-diarylsubstituted thioureas 20 and
thioacetamides 21 a series of heterocyclic analogous of N,N -per-
arylated phenylene-1,4-diamines and benzidines was obtained.
These compounds represent, as studied by DSC measurements, a
new class of hole transporting materials with high thermal stability (Scheme 1) were prepared, e.g., from substituted aryl ha-
and high tendency to form stable amorphous states. Moreover, some
of the new compounds are, as measured by cyclic voltammetry, eas-
ily reversibly oxidized indicating the formation of persistent radical
diarylamines 2 and 1,4-dihalobenzenes 5 or 4,4 -dihalobi-
ions. Such compounds, which are, in general, completely substitut-
lides 1 and N,N -diaryl-substituted phenylene-1,4-di-
amines 3 or benzidines 4 or, alternatively, from
phenyls 6 by means of a C N coupling reaction accom-
ed by aryl groups at their heterocyclic moieties, have been success-
plished by copper9 or palladium10 catalysts.
fully used as hole-transport materials in OLEDs.
Another concept favoring the amorphous state consists in
replacing aryl or phenylene groups in compounds 9 and
10 by heterocyclic moieties, such as thienyl or thienylene.
Thus, N,N -perarylated 2,5-diaminothiophenes 1111 and
5,5 -diamino-2,2 -bithiophenes 1212 as heterocyclic ana-
logues of the 1,4-phenylenediamines 9 and benzidines 10
were prepared from diarylamines 2 and 2,5-dibro-
mothiophene (7) or 5,5 -dibromo-2,2 -bithiophene (8) us-
ing palladium catalysts.
Key words: heterocyclization, hole transport materials, N-perary-
lated 2-aminothiophenes, N-perarylated 2-aminothiazoles
Because of their electrical properties N,N ,N -perarylated
1,3,5-triaminobenzene of the so-called starburst series1
and N,N -perarylated phenylene-1,4-diamines 92 and ben-
zidines 103 are of interest for organic light-emitting diodes
(OLEDs),4 organic field-effect transistors,5 organic solar
cells,6 or organic recording and storage media.7
Although metal-catalyzed coupling reactions reach, in
common, high yields they lack from residual metal impu-
rities. This is detrimental to electric and optical properties.
Purification is an urgent need but a time and cost consum-
ing procedure.
H
H
2 Ar1-Hal
+
Ar2
N
N
Ar2
1
Ar1
Ar2
Ar1
Ar2
n
3, 4
Therefore a simple heavy metal-free synthesis for N,N -
perarylated diamines 9 and 10 or their heterocyclic ana-
logues 11 and 12 is highly favoured. Although such routes
for the carbocyclic compounds 9–10 are not in sight today
we will present a simple route to several derivatives of
their heterocyclic sulphur analogues. This route allows the
synthesis of thiophene analogues 11 and 12 of the phe-
nylene-1,4-diamine and benzidine derivatives 9 and 10, as
well as the synthesis of hitherto unknown thiazole ana-
logues. The route is based on well-known methods for
preparing amino-substituted thiophenes and thiazoles by
heterocyclization procedures and requires dedicated
educts, such as halomethyl ketones, like the compounds
13–15, as well as N-diarylamines and N,N -(diaryl)di-
amines of the general structure 2 4. Whereas the amines
2, 3 and 4 used are commercially available, the halometh-
yl ketones 13–15 have to be synthesized, as far as possible
from commercially available, simple halo-free precursors.
N
N
Hal
Hal
+
+
n
9, 10
Ar1
n
5, 6
2
N
H
Ar2
Ar1
Ar1
2
N
N
Hal
Hal
S
S
Ar2
2
n
Ar
n
11, 12
7, 8
Scheme 1
For all applications materials with excellent glass-form-
ing tendency and easy formation of radical ions are advan-
tageous. Both properties correlate to the molecular
structure. Thus, the glass-forming tendency can be in-
creased by increasing the number of conformers.8 In this
respect substituted aryl moieties, such as m-tolyl or naph-
Synthesis 2002, No. 9, 01 07 2002. Article Identifier:
1437-210X,E;2002,0,09,1268,1276,ftx,en;C11102SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881

PAPER
Heterocyclic Analogues as a New Class of Hole Transport Materials
1269
Thus, the dibromodiketones 14 and 15 were prepared to the formation of intermediate N-pivaloylthioureas 18
from 1,2-dibenzoylethylene or 1,4-diacetylbenzene, re- from which the N-diarylthioureas 20 were obtained by re-
spectively, by reaction with elemental bromine in acetic action with concentrated aqueous hydrochloric acid. The
acid.13
subsequent reaction of these thioureas 20 with the bro-
moketones 13–15 (Figure 1), performed in ethanol, DMF,
or acetic anhydride, yields N-disubstituted 2-aminothiaz-
oles 22 as well as bisthiazoles 23 and 24, respectively.
O
Br
O
H
R4
O
R4
R5
By an analogous sequence, the reaction of the diary-
lamines 2 with acetyl chlorides of the general structure 17
gave rise to the formation of N-diarylsubstituted aceta-
mides 19. These compounds were transformed by reaction
with P2S5 or Lawesson’s reagent to their corresponding N-
diarylsubstituted thioacetamides 21 and, subsequently,
into corresponding bithiophenes 25 and 26 as well as into
N-disubstituted 2-aminothiophenes 27 by reaction with
the bromoketones 13–15. The last step of this reaction se-
quence was performed in ethanol, DMF, or acetic anhy-
dride and has a strong analogy to the simple Hantzsch
O
Br
H
Br
Br
H
R4
O
Br
15
13
14
Figure 1
Products were obtained as depicted in Scheme 2. Thus,
the diarylamines 2 were allowed to react with pivaloyl-
isothiocyanate 16, simply prepared in situ from pivaloyl
chloride and potassium rhodanide. This reaction gave rise
R4
+ 13
N
R5
Ar2
S
N
Ar1
22
C(CH3)3
R4
R4
S
NH2
+ 14
HN
O
N
N
HCl
Ar2
Ar2
Ar2
N
S
Ar2
N
Ar1
S
S
N
N
Ar1
Ar1
Ar1
20
23
18
(H3C)3C
Ar2
Ar2
N
O
16
N
N
Ar1
Ar1
N
N
C
S
+ 15
S
S
R5
R5
R3
24
Ar2
H
N
Ar2
Ar2
N
R3
Ar1
N
+ 15 Ar1
Ar1
2
S
S
R3
Cl
R5
R5
25
17
O
R4
R4
S
R3
R3
N
R3
N
R3
+ P2S5
+ 14
Ar2
Ar2
Ar2
Ar2
N
S
S
O
N
Ar1
Ar1
Ar1
Ar1
21
19
26
R4
R3
N
+ 13
R5
Ar2
S
Ar1
27
Scheme 2
Synthesis 2002, No. 9, 1268–1276 ISSN 0039-7881 © Thieme Stuttgart · New York

1270
J. Schumann et al.
PAPER
route for the synthesis of thiazoles.14 This method was ap- ably, the low solubility of the N,N -diphenylbenzidine
plied for the time by us for the synthesis of N-dialkylsub- (29) in the solvents used prevents the reaction with piv-
stituted 2-aminothiophenes more than four decades ago.15 aloylisothiocyanate (16).
By means of these procedures the N-diaryl-substituted 2- From the compounds 30, 32, and 33 the bis-thioureas 34
aminothiazoles 22 and 2-aminothiophenes 27 as well as (Scheme 3) as well as the bis-thioacetamide derivatives
the N,N -peraryl-substituted 2,2 -diamino-5,5 -bithiazoles 36 and 37 were obtained in the same way as described
23, 5,5 -diamino-2,2 -bithiophenes 26, 1,4-bis[(2-amino- above. Their transformation into the bis-thiazoles 38 and
1,3-thiazol)-4-yl]benzenes 24 and 1,4-bis(2-amino-thien- the bis-thiophenes 40 and 41 was performed by reaction
4-yl)benzenes 25 have been prepared.
with the bromoketones 13 in DMF at reflux temperature.
A similar reaction sequence can be used for the synthesis Due to the N-bound aryl groups the solubility of the prod-
of the heterocyclic compounds 38–41. As starting materi- ucts obtained is high enough in most polar organic sol-
als, besides the bromo compounds 13-15, the N,N’-diphe- vents that, in general, the synthesis can be performed
nyl-substituted diamines 28 and 29 were used which are without difficulties.
commercially available. They were allowed to react first
with pivaloylisothiocyanate (16) or with acetyl chlorides
17. From the expected compounds 30–33 the bis-(N-piv-
aloyl)-substituted bis-thiourea 30 as well as the bis-aceta-
mides 32 and 33 were obtained only (see Table 1). The
bis-(N-pivaloyl)-substituted bis-thiourea 31 was not
The structure of the compounds prepared was confirmed
by means of elemental analyses and spectroscopic data.
Thus, in the mass spectra all compounds exhibit an intense
peak for the molecular ion M+ or for the MH+ ion. Al-
though in the 1H and 13C NMR spectra, as seen from the
data collected in Table 1, only less characteristic signals
formed, however, so that the corresponding consecutive
can be detected, their positions and intensities are in
products 35 and 39 could not be obtained until now. Prob-
agreement with the predicted structure.
C(CH3)2 (H3C)2C
R4
R4
O
S
O
S
R5
R5
NH
N
HN
N
N
N
N
NH2
N
H2N
S
S
S
S
N
n
N
n
n
H
H
30, 31
34, 35
38, 39
N
N
n
R4
R4
28, 29
R5
R5
R3
R3
R3
R3
R3
R3
O
O
S
S
S
S
N
N
N
N
N
N
n
n
n
28, 30, 32, 34, 36, 38, 40: n = 1
29, 31, 33, 35, 37, 39, 41: n = 2
32, 33
36, 37
40, 41
Scheme 3
Table 1 NMR Spectroscopic Data of the Heteroaromatic Compounds Prepared
Com- Ar1
pound
Ar2
R3
R4
R5
1H NMR (CDCl3), [ppm]
13C NMR (CDCl3), [ppm]
22a
22b
23
Phenyl Phenyl
Phenyl Phenyl
Phenyl Phenyl
Phenyl Phenyl
-
Phenyl
H
6.86 (s, 1 H, hetarom.), 7.20–7.28 (m, 4 H, 126.7, 126.8, 127.2, 128.8, 129.6,
arom.), 7.33–7.45 (m, 9 H, arom.), 7.81 (d, 130.6, 134.5, 135.9, 146.3, 152.8,
2 H, arom.)
169.7
-
-
-
Phenyl Phenyl 7.19–7.28 (m, 10 H, arom.), 7.37 (t, 4 H,
arom.), 7.43–7.47 (m, 4 H, arom.), 7.50
(dd, 2 H, arom.)
124.2, 125.6, 127.7, 127.3, 127.4,
128.0, 128.5, 128.9, 129.4, 129.5,
132.5, 135.2, 145.0, 145.9, 166.1
Phenyl
-
7.21 (d, 8 H, arom.), 7.32–7.42 (m, 18 H, 113.8, 126.9, 128.8, 129.2, 129.3,
arom.), 7.68 (m, 4 H, arom.)
129.4, 130.6, 135.6, 141.7, 145.8
150.8
24
-
Phenyl 6.86 (s, 2 H, arom.), 7.22 (t, 4 H, arom.),
105.4, 126.8, 126.9, 127.3, 130.6,
7.36–7.45 (m, 16 H, arom.), 7.82 (s, 4 H, 135.2, 146.3, 152.6, 169.7
arom.)
Synthesis 2002, No. 9, 1268–1276 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Heterocyclic Analogues as a New Class of Hole Transport Materials
1271
Table 1 NMR Spectroscopic Data of the Heteroaromatic Compounds Prepared (continued)
Com- Ar1
pound
Ar2
R3
R4
-
R5
H
1H NMR (CDCl3), [ppm]
13C NMR (CDCl3), [ppm]
25
Phenyl Phenyl
Phenyl
6.83–6.90 (m, 8 H, arom.), 6.92 (s, 2 H,
hetarom.), 6.91–7.04 (m, 16 H, arom.),
7.08–7.13 (m, 10 H, arom.)
119.4, 121.5, 122.1, 126.7, 127.7,
128.3, 128.7, 129.7, 134.7, 135.1,
137.1, 141.0, 146.0, 147.3
26
Phenyl Phenyl
Phenyl Phenyl
Phenyl Phenyl
-
6.78 (d, 4 H, arom.), 6.84–6.96 (m, 18 H, 121.5, 122.1, 126.5, 126.6, 127.4,
arom.), 7.02–7.15 (m, 16 H, arom.), 7.24
(t, 2 H, arom.)
127.8, 128.7, 128.8, 129.7, 130.6,
134.7, 135.4, 137.9, 140.9, 145.7,
147.0
27a
27b
Phenyl Phenyl
Phenyl Phenyl
H
6.92 (s, 1 H, hetarom.), 6.90–6.94 (m, 4 H, 120.8, 122.7, 123.3, 127.9, 127.8,
arom.), 6.98–7.08 (m, 6 H, arom.), 7.15–
7.21 (m, 10 H, arom.)
128.9, 129.1, 129.8, 130.0, 130.9,
136.0, 138.0, 138.4, 142.6, 147.3,
148.6
Phenyl Phenyl Phenyl 6.83 (d, 2 H, arom.), 6.89–7.00 (m, 6 H,
arom.), 7.03–7.10 (m, 6 H, arom.), 7.13–
122.5, 123.0, 127.2, 127.3, 127.8,
128.1, 128.5, 129.1, 129.5, 130.0,
130.5, 131.6, 135.1, 135.8, 136.4,
7.24 (m, 9 H, arom.), 7.30–7.37 (m, 4 H,
arom.), 7.60 (t, 2 H, arom.), 7.69 (d, 1 H, 136.9, 137.9, 140.1, 145.1, 148.1
arom.)
27c
27d
Phenyl 1-Naphthyl Phenyl Phenyl
H
6.77 (d, 2 H, arom.), 6.83 (t, 1 H, arom.), 118.9, 120.1, 121.3, 125.5, 126.6,
6.87–6.99 (m, 4 H, arom.; 1 H, hetarom.), 126.7, 126.8, 127.0, 127.5, 127.6,
7.06–7.16 (m, 10 H, arom.), 7.28–7.35 (m, 127.8, 128.9, 129.0, 129.1, 129.8,
2 H, arom.), 7.54 (d, 1 H, arom.), 7.62 (d, 129.9, 131.1, 131.2, 135.9, 136.3,
1 H, arom.), 7.73 (d, 1 H, arom.)
137.8, 138.0, 142.6, 143,8, 148.4,
151.3
Phenyl 2-Naphthyl Phenyl Phenyl Phenyl 6.88–7.00 (m, 2 H, arom.), 7.03–7.14 (m, 118.6, 122.7, 122.9, 123.2, 125.0,
8 H, arom.), 7.18–7.27 (m, 9 H, arom.),
7.29–7.43 (m, 4 H, arom.), 7.64 (t, 2 H,
arom.), 7.73 (d, 2 H, arom.)
126.9, 127.2, 127.4, 127.7, 127.9,
128.1, 128.2, 128.6, 128.9, 129.2,
129.6, 130.0, 130.4, 130.5, 131.6,
134.9, 135.1, 135.8, 136.5, 136.8,
138.0, 140.2, 145.0, 145.8, 148.0
38
-
-
-
-
-
-
-
Phenyl Phenyl 7.23 (d, 4 H, arom.), 7.27–7.31 (m, 6 H,
arom.), 7.32–7.42 (m, 8 H, arom.), 7.45–
124.0, 125.6, 126.8, 127.3, 128.0,
128.4, 128.8, 129.4, 129.5, 130.6,
7.48 (m, 4 H, arom.), 7.55 (d, 4 H, arom.), 132.3, 135.3,141.7, 144.6, 145.9,
7.60 (s, 4 H, arom.), 7.61 (t, 4 H, arom.)a
162.3, 165.7a
40a
40b
Phenyl Phenyl
H
6.66 (s, 4 H, arom.), 6.83–6.90 (m, 8 H,
119.3, 120.0, 121.3, 123.8, 126.8,
arom.; 2 H, hetarom.), 6.98–7.06 (m, 6 H, 126.9, 127.9, 128.1, 128.8, 130.0,
arom.), 7.09–7.19 (m, 16 H, arom.)
135.1, 136.8, 136.9, 141.6, 142.1,
146.8, 148.2
Phenyl Phenyl Phenyl 6.73 (s, 4 arom. H), 6.81 (d, 4 arom. H),
120.1, 121.3, 123.8, 126.5, 126.9,
6.86 (t, 2 arom. H), 6.93–7.00 (m, 12 arom. 127.2,127.5, 127.7, 128.2, 128.8,
H), 7.04–7.19, (m, 22 arom. H)
129.4, 129.8, 130.9, 134.5, 135.3,
136.1, 137.1, 138.8, 142.0, 144.5,
148.0
41a
41b
-
-
-
-
Phenyl Phenyl
H
6.85–6.98 (m, 12 H, arom.; 2 H, hetarom.), 120.4, 124.6, 128.3, 129.4, 136.0,
7.02–7.12 (m, 10 H, arom.), 7.14–7.26 (m, 138.9, 146.1, 151.3
14 H, arom.), 7.19 (t, 2 H, arom.)
Phenyl Phenyl Phenyl 6.83 (d, 4 H, arom.), 6.90 (t, 4 H, arom.)
6.94–6.98 (m, 8 H, arom.), 7.01 (t, 2 H,
121.8. 122.0, 122.5, 126.6, 126.7,
127.0, 127.2, 127.6, 127.9, 128.3,
arom.), 7.03–7.10 (m, 12 H, arom.), 7.12– 128.9, 129.4, 129.9, 131.0, 134.5,
7.21 (m, 14 H, arom.), 7.32 (d, 4 H, arom.) 134.6, 135.2, 135.8, 136.3, 137.3,
139.6, 144.3, 146.5, 147.3
a In HMPT-d18.
DSC was used to investigate the tendency of the new ma- melting temperatures Tms, and the decomposition temper-
terials to form the amorphous state. These data are com- atures Tds were measured under nitrogen atmosphere with
1
piled in Table 2. The glass transition temperatures Tgs, the a heating rate of 5 K min .
Synthesis 2002, No. 9, 1268–1276 ISSN 0039-7881 © Thieme Stuttgart · New York

1272
J. Schumann et al.
PAPER
Table 2 Characteristic Substance Data of Some of the Compounds Prepared
a
a
a
Com- Ar1
pound
Ar2
R3
R4
R5
Tm
Td
Tg
Typeb Eox [V]c
Molecular
Formula
EIMS [m/z (%)]
405.4 (MH+, 100)
22b
23
Phenyl Phenyl
Phenyl Phenyl
-
-
Phenyl Phenyl
223
232
268
391
-
A
B
1.14 (ir)
C27H20N2S
Phenyl
-
72
0.95 (qr), C42H30N4S2 655.4 (MH+, 100)
1.00 (qr)
24
Phenyl Phenyl
Phenyl Phenyl
Phenyl Phenyl
Phenyl Phenyl
Phenyl Phenyl
-
-
-
Phenyl
279
241
262
102
120
64
386
384
368
230
434
252
330
418
65
82
87
20
57
51
61
91
B
B
B
C
B
C
B
B
1.03 (qr) C36H26N4S2 579.4 (MH+, 100)
1.05 (qr) C50H36N2S2 728.5 (M+, 100)
25
Phenyl
Phenyl
26
Phenyl Phenyl
Phenyl Phenyl
-
0.64 (r)
1.00 (ir)
0.95 (r)
1.10 (ir)
0.73 (r)
C56H40N2S2 804.5 (M+, 100)
27a
27b
27c
27d
38
H
C26H21NS
C34H25NS
C32H23NS
C38H27NS
404.3 (MH+, 100)
479.3 (MH+, 100)
454.4 (MH+, 100)
529.4 (MH+, 100)
Phenyl Phenyl Phenyl
Phenyl 1-Naphthyl Phenyl Phenyl
H
Phenyl 2-Naphthyl Phenyl Phenyl Phenyl
198
302
-
-
-
-
-
-
-
-
-
Phenyl Phenyl
1.01(r),
C48H34N4S2 731.4 (MH+, 100)
1.23 (qr)
40a
40b
41b
Phenyl Phenyl
H
263
317
276
283
410
431
83
118
114
B
B
B
0.75(qr), C50H36N2S2 728.3 (M+, 100)
1.13 (qr))
Phenyl Phenyl Phenyl
Phenyl Phenyl phenyl
0.75 (r),
1.07 (r)
C62H44N2S2 880.5 (M+, 100)
0.94 (qr) C68H48N2S2 956.5 (M+, 100)
a Tm: melting point, Td: decomposition point, Tg: glass transition point, all data in °C.
b Type A: recrystallization at cooling, type B: no crystallization at cooling, recrystallization above Tg, type C: no crystallization at cooling, no
crystallization above Tg.
c ir: irreversible potential; pr: quasi-reversible potential; r: reversible potential.
In order to prove that the observed Tgs are real glass tran-
sition temperatures and not originating from other relax-
ation processes, the measurements were repeated several
times and corresponding transition energies were estimat-
1
ed. They were generally in the range of 0.2-0.3 J g 1 K .
As it can be seen from Table 2, melting temperatures Tm
and decomposition temperatures Td depend, similarly as
the decomposition temperatures Tg, significantly on the
substitution pattern at the heterocyclic moiety. Besides
compound 22b, all other compounds studied are able to
attain the amorphous state after cooling the melt. In some
cases, the obtained glasses are rather stable and do not re-
crystallize even after repeated heating beyond glass tran-
sition temperature (Type B). In some cases, however,
some glasses recrystallize during the heating procedure
(Type C). Compounds of type B are expected to be good
candidates for electrical conducting materials.
All the compounds studied exhibit, as measured by cyclic
voltammetry and exemplified with to compounds in
Figure 2 , low oxidation potentials, but not all potentials
are reversible. This means, that under the conditions ap-
plied the radical cations formed are not very stable. As
demonstrated in a forthcoming paper in detail, such radi-
Figure 2 Cyclic voltammograms of compound 27b (a) and 26a (b),
measured in acetonitrile/Bu4PF6/Pt versus SCE
cal ions give rise to the formation of the corresponding
dimers.
Synthesis 2002, No. 9, 1268–1276 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Heterocyclic Analogues as a New Class of Hole Transport Materials
1273
fluxed until the generation of HCl decreased. After cooling, the
mixture was poured in ice-water (1 L), the product precipitated was
isolated by suction and recrystallized from EtOH. The following
products were obtained:
The compounds, which exhibit reversible oxidation po-
tentials, were investigated as hole transport materials in
organic luminescence diodes. Such compounds are, in
general, aryl substituted at their thiophene 5-position.
2,N,N-Triphenylacetamide (19a)
The diodes were manufactured by vacuum-evaporation
on an ITO-coated glass substrate. The effectiveness of the
hole transport ability of the compounds studied was esti-
mated by measuring the luminescence quantum yield of
Alq3 as function of the voltage applied. The results ob-
tained were compared to OLEDs manufactured with stan-
dard transport materials such as 1-Naphdata or -NPD.16
The data which will be published in detail in a forthcom-
ing paper,17 demonstrate that an OLED in which both the
standard materials were substituted by, e.g., the com-
pounds 40b and 41b exhibit nearly the same or a slight
better luminance efficiency as an OLED manufactured
with standard materials.
Compound 19a has been synthesized according to the general pro-
cedure from diphenylamine (2a) and phenacetylchloride (17a) in a
yield of 44.8 g (78%).
Mp 71–72 °C (Lit.20 72 °C).
1H NMR (CDCl3): = 3.55 (s, 2 H, CH2), 7.09 (d, 2 H, CH), 7.17–
7.42 (m, 13 H, CH).
N-Phenyl-N-phenacetyl-1-naphthylamine (19b)
Compound 19b has been synthesized according to the general pro-
cedure from 1-(N-phenyl)naphthylamine (2b) and phenacetylchlo-
ride (17a) in a yield of 28.0 g (83%).
Mp 85–88 °C.
1H NMR (CDCl3): = 3.50 (s, 2 H, CH2), 6.96 (m, 2 H, CH), 7.11–
7.35 (m, 9 H, CH), 7.43- 5.53 (m, 3 H, CH), 7.80-7.87 (m, 3 H, CH).
Hence, the N-perarylated 2-aminothiophenes and 2-ami-
nothiazoles of the structure 23–26 and 38–41, easily avail-
able by a Hantzsch-type reaction from mono- or
bifunctional N,N-diarylsubstituted thioureas or thioaceta-
mides and -haloketones, represent a new class of easily
oxidizable compounds with a high tendency to form
amorphous glasses in which the charged species formed
by electrochemical oxidation exhibit a high mobility giv-
ing rise to high quantum yields of the Alq3 luminescence.
N-Phenyl-N-phenacetyl-2-naphthylamine (19c)
Compound 19c has been synthesized according to the general pro-
cedure from 2-(N-phenyl)naphthylamine (2c) and phenacetylchlo-
ride (17a) in a yield of 28.0 g (83%).
Mp 129-130 °C.
1H NMR (CD3CN): = 3.68 (s, 2 H, CH2), 7.13–7.16 (m, 2 ArH),
7.22-7.31 (m, 4 ArH), 7.35–7.44 (m, 5 ArH), 7.31 (q, 2 ArH), 7.78–
7.83 (m, 2 ArH), 7.86-7.89 (m, 2 ArH).
The following apparatus and analytical techniques were used: Melt-
ing points: Boetius hot-stage microscope, corrected, IR: Philips
FTIR spectrometer PU 9624 (in potassium bromide pellets), NMR:
Varian 300 MHz spectrometer Gemini 300 or JEOL 200 MHz spec-
trometer JNM FX 200, Elemental analysis data: LECO analyzer
CHNS 932, MS: AMO spectrometer 402 (70 eV, EI), Cyclic volta-
mmetry: Autolab instrument PGSTAT 20, The measurements were
performed under argon in MeCN containing 0.1 M Bu4PF6 as sup-
porting electrolyte with a scan rate of 0.1 V s 1 using a platinum
working electrode, a platinum counter electrode and, a sat. Calomel
reference electrode, Mass spectra: ESI, LCQ, Finnigan MAT, DTA/
TGA: STA 1500, Polymer Laboratories, U.S.A, DSC: Netzsch DSC
200.
N,N -Diphenyl-N,N -bis(2-phenacetyl)phenylene-1,4-diamine
(32)
By analogy to the previous procedure N,N’-(diphenyl)phenylene-
1,4-diamine 28 (0.1 mol, 26.0 g) was allowed to react with phenace-
tylchloride (17a, 0.2 mol, 30.8 g). The product was obtained in a
yield of 30.3 g (61%).
Mp 190 °C.
1H NMR (DMSO-d6), = 3.75 (s, 4 H, CH2), 7.05 (d, 4 H, CH),
7.15–745 (m, 20 H, CH).
Anal. Calcd for C34H28N2O2 (496.6): C, 82.3; H, 5.6; N, 5.6. Found:
C, 82.1; H, 5.6; N, 5.5.
N,N -Diphenyl-N,N -bis(2-phenacetyl)benzidine (33)
By analogy to the previous procedure N,N -(diphenyl)benzidine
(29, 0.1 mol, 33.6 g) was allowed to react with phenacetylchloride
(17a, 0.2 mol, 30.8 g). The product was obtained in a yield of 33.7
g (59%).
1,2-Dibenzoyl-1,2-dibromoethane (14)
To a 10 °C cooled soln of 1,2-dibenzoylethene (0.01 mol, 23.6 g) in
HOAc (150 mL), bromine (0.01 mol, 18 g) was added dropwise
with stirring. After 30 min, the mixture was poured into ice-water,
the precipitated product was isolated by suction and recrystallized
from EtOH.
Mp 155 °C.
1H NMR (CDCl3): = 3.60 (s, 4 H, CH2), 7.11 (d, 4 H, CH), 7.19 (t,
4 H, CH), 7.26 (t, 4 H, CH), 7.30–7.44 (m, 12 H, CH), 7.62–7.69
(m, 4 H, CH).
Yield 25.8 g (65%).
Mp 178 °C (Lit.18 178 °C).
Anal. Calcd for C40H32N2O2 (572.7): C, 83.9; H, 5.6; N, 4.9. Found:
C, 82.8; H, 5.7; N, 4.7.
1,4-Bis-(bromoacetyl)benzene (15)
By analogy to the previous procedure 1,4-diacetylbenzene (0.01
mol, 16.2 g) was allowed to react with Br2 (0.02 mol, 32.0 g). The
product was obtained in a yield of 21.8 g (68%).
N,N-Diphenylthiourea (20)
To a refluxing mixture of potassium thiocyanate (0.31 mol, 30.1 g)
in acetone (200 mL) pivaloylic chloride (0.3 mol, 36.0 g), followed
by a soln of a diarylamine 2 (0.3 mol) in acetone (150 mL) was add-
ed under stirring. After cooling to r.t. the mixture was diluted with
H2O (600 mL), containing concd HCl (50 mL). The solid formed
was decanted and mixed with concd HCl (100 mL). The resulting
mixture was refluxed for 15 min and poured in ice-water (2 L). The
product precipitated was grinded with EtOH, isolated by suction,
Mp 168 °C (Lit.19 173 °C).
2,N,N-Triaryl-substituted Acetamides 19; General Procedure
To a stirred soln of a diarylamine 2 (0.1 mol) in anhyd dioxane (200
mL), in a three-necked flask fitted with dropping-funnel, reflux-
condenser and an inlet for nitrogen, phenacetylchloride [(17), (0.2
mol, 30.8 g)] was added dropwise at r.t. Then, the mixture was re-
Synthesis 2002, No. 9, 1268–1276 ISSN 0039-7881 © Thieme Stuttgart · New York

1274
J. Schumann et al.
PAPER
N,N -diphenyl-N,N -bis-(phenylthioacetyl)benzidine (37)
By analogy to the previous procedure N,N -diphenyl-N,N -bis-(phe-
nylthioacetyl)benzidine (33, 28.6 g, 0.05 mol) was allowed to react
with Lawesson’s reagent (0.06 mol, 24.4g) in 1,2-dimethoxyethane
(200 mL). The product was obtained in a yield of 21.1 g (70%).
and purified by twofold recrystallization from EtOH. The product
was obtained in a yield of 50.7 g (64%).
Mp 212 °C. (Lit.21 212 °C).
N,N -Bis-(thiocarbamido)-N,N -(diphenyl)phenylene-1,4-di-
amine (34)
Mp 190–194 °C.
By analogy to the previous procedure N,N -(diphenyl)phenylene-
1,4-diamine (28, 39.0 g, 0.15 mol) was allowed to react with piv-
aloylisothiocyanate (0.15 mol) prepared in situ from potassium
thiocyanate and pivaloylchloride in acetone. The product was ob-
tained in a yield of 31.0 g (55%).
1H NMR (DMSO-d6): = 4.12 (s, 4 H, CH2), 7.08 (d, 4 ArH), 7.16–
7.50 (m, 20 ArH), 7.66 (t, 4 ArH).
Anal. Calcd for C40H32N2O2 (604.8): C, 79.5; H, 5.3; N, 4.6; S, 10.6.
Found: C, 78.7; H, 5.4; N, 4.4; S, 10.4.
Mp 177 °C.
2-(N,N-Diarylamino)thiazoles 22; General Procedure
A soln of N,N-diphenylthiourea (20, 0.01 mol, 2.28 g) and of the
corresponding bromoketone 13 (0.01 mol) in EtOH (100 mL) was
refluxed for 6 h. After cooling the mixture was diluted with ice-wa-
ter (200 mL) and the precipitate formed was isolated by filtration,
followed by recrystallization from EtOH. The following products
were obtained:
Anal. Calcd for C30H34N4O2S2 (546.7): C, 65.9; H, 6.3; N, 10.3; S,
11.7. Found: C, 64.2; H, 6.3; N, 10.8; S, 10.9.
N,N-Diarylthioacetamides 21; General Procedure
A mixture of a N,N-disubstitituted acetamide (19, 0.1 mol), Lawes-
son’s reagent (0.06 mol, 24.4 g), and 1,2-dimethoxyethane (200
mL) was stirred at 100 °C for 5 h. The product, precipitated after
cooling, was isolated by suction followed by washing with a mix-
ture of Et2O CH2Cl2 (1:1). The following products were obtained:
2-(N,N-diphenylamino)-3-phenylthiazole (22a)
From N,N-diphenylthiourea (20) and phenacylbromide (13a) in a
yield of 2.5 g (76%).
2,N,N-triphenylthioacetamide (21a)
From 19a in a yield of 27.3 g (90%).
Mp 120 °C (Lit.22 120 °C).
Anal. Calcd for C21H16N2S (328.4): C, 76.8; H, 4.9; N, 8.5; S, 9.8.
Found: C, 77.1; H, 5.2; N, 8.7; S, 9.8.
Mp 142–144 °C.
1H NMR (CDCl3): = 4.30 (s. 2 H. CH2), 7.05–7.10 (m, 4 ArH),
7.17–7.21 (m, 3 ArH), 7.23–7.32 (m, 6 ArH), 7.37 (t, 2 ArH).
2-(N,N-diphenylamino)-3,4-diphenylthiazole (22b)
From N,N-diphenylthiourea (20) and 2-bromo-1,2-diphenyletha-
none (13b) in a yield of 3.3 g (82%).
Anal. Calcd for C20H17NS (303.4): C, 79.2; H, 5.6; N, 4.6; S, 10.6.
Found: C, 79.0; H, 5.8; N, 4.6; S, 10.4.
Mp 223 °C.
N-Phenyl-N-(phenylthioacetyl)1-naphthylamine (21b)
From 19b in a yield of 27.9 g (79%).
Anal. Calcd for C27H20N2S (404.5): C, 80.2; H, 5.0; N, 6.9; S, 7.9.
Found: C, 79.8; H, 5.0; N, 7.1; S, 7.4.
Mp 100–103 °C.
2,2 -Bis(N,N-diphenylamino)-4,4 -diphenyl-5,5 -bithiazole (23)
By analogy to the previous procedure N,N-diphenylthiourea (20,
0.02 mol, 4.6 g) was allowed to react with 1,2-dibenzoyl-1,2-dibro-
moethane (14, 0.01 mol, 4.0 g). The product was obtained after re-
crystallization from DMF in a yield of 4.3 g (63%).
1H NMR (CD3CN): = 3.87 (s, 1 H, CH2), 4.18 (s, 1 H, CH2), 6.93
(t, 2 Ar H), 7.08–7.17 (m, 4 ArH), 7.30–7.38 (m, 3 ArH), 7.42 (t, 1
ArH), 7.58 (dd, 2 ArH), 7.76–7.84 (m, 3 ArH), 7.91 (d, 1 ArH),
8.10 (d 1 ArH).
Anal. Calcd for C24H19NS (353.5): C, 81.6; H, 5.4; N, 4.0; S, 9.1.
Found: C, 81.5; H, 5.4; N, 4.3; S, 9.1.
Mp 232 °C.
Anal. Calcd for C42H30N4S2 (654.8): C, 77.1; H, 4.6; N, 8.6; S, 9.8.
Found: C, 76.8; H, 5.2; N, 8.5; S, 9.3.
N-Phenyl-N-(phenylthioacetyl)2-naphthylamine (21c)
From 19c in a yield of 14.0 g (40%).
1,4-Bis{[2-(N,N -diphenylamino)-1,3-thiazol]-4-yl}benzene (24)
By analogy to the previous procedure N,N-diphenylthiourea (20,
0.02 mol, 4.6 g) was allowed to react with 1,4-bis-(bro-
moacetyl)benzene (15, 0.01 mol, 3.2 g). The product was obtained
after recrystallization from DMF in a yield of 3.3 g (57%).
Mp 112–113 °C.
1H NMR (MeCN): = 4.24 (s, 2 H, CH2), 7.13–7.16 (m, 2 ArH),
7.22–7.30 (m, 4 Ar H), 7.35–7.44 (m, 5 ArH), 7.50 (q, 2 ArH),
7.78–7.80 (m, 2 ArH), 7.8–7.88 (m, 2 ArH).
Anal. Calcd for C24H19NS (353.5): C, 81.6; H, 5.4; N, 4.0; S, 9.1.
Found: C, 81.0; H, 5.5 N; 4.3, S, 9.4.
Mp 279 °C.
Anal. Calcd for C36H26N4S2 (578.8): C, 74.7; H, 4.5; N, 9.7, S, 11.1.
Found: C, 74.4; H, 4.6; N, 9.7; S, 10.9.
N,N -Bis-(phenylthioacetyl)-N,N -(diphenyl)phenylene-1,4-di-
amine (36)
1,4-Bis{[2-(N,N-diphenylamino)-3-phenyl]-4-thienyl}benzene
(25)
By analogy to the previous procedure N,N,2-triphenylthioacetamide
(21a, 0.02 mol, 6.06 g) was allowed to react with 1,4-bis(bro-
moacetyl)benzene (15, 0.01 mol, 3.2 g). The product was obtained
after recrystallization from DMF in a yield of 3.8 g (52%).
By analogy to the previous procedure N,N -bis(phenacetyl)-N,N -
(diphenyl)phenylene-1,4-diamine (32, 24.8 g, 0.05 mol) was al-
lowed to react with Lawesson’s reagent (0.06 mol, 24.4 g) in 1,2-
dimethoxyethane (200 mL). The product was obtained in a yield of
16.9 g (79%).
Mp 223–227 °C.
1H NMR (CDCl3): = 4.25 (s, 4 H, CH2), 6.97–7.10 (m, 8 ArH),
7.14–7.20 (m, 4 ArH), 7.22 (s, 4 ArH), 7.25–7.35 (m, 8 ArH).
Mp 241 °C.
Anal. Calcd for C50H36N2S2 (728.5): C, 82.4; H, 4.9; N, 3.8; S, 8.8.
Found: C, 81.7; H, 5.2; N, 3.9; S, 9.4.
Anal. Calcd for C34H28N2S2 (528.7): C, 77.3; H, 5.3; N, 5.3; S, 12.1.
Found: C, 77.7; H, 5.2; N, 4.9; S, 11.5.
Synthesis 2002, No. 9, 1268–1276 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Heterocyclic Analogues as a New Class of Hole Transport Materials
1275
2,2 -Bis(N,N-diphenylamino)-3,3 ,4,4 -tetraphenyl-5,5 -
bithiophene (26)
N,N -Diphenyl-N,N -bis(3,4-diphenyl-2-thienyl)-phenylene-1,4-
diamine (40a)
By analogy to the previous procedure N,N,2-triphenylthioacetamide
(21a, 0.02 mol, 6.1 g) was allowed to react with 1,2-dibenzoyl-1,2-
dibromoethane (14, 0.01 mol, 4.0 g)] in DMF (100 mL). The prod-
uct was obtained by pouring the reaction mixture into H2O EtOH
(1:1) (200 mL) and recrystallization from DMF in a yield of 3.0 g
(37%).
A mixture of N,N -diphenyl-N,N -bis(phenylthioacetyl)phenylene-
1,4-diamine (36, 0.01 mol, 5.28 g) and phenacylbromide (13a, 0.02
mol, 4.0 g) in DMF (100 mL) was stirred for 10 h at 100 °C. After
cooling, the mixture was diluted with ice-water (250 mL) and the
precipitate formed was isolated by filtration, followed by recrystal-
lization from DMF. The product was obtained in a yield of 3.3 g
(45%).
Mp 262 °C.
Mp 263 °C.
Anal. Calcd for C56H40N2S2 (805.1): C, 83.6; H, 5.0; N, 3.5; S, 8.0.
Found: C, 82.3; H, 5.3; N, 3.2; S, 7.9.
Anal. Calcd for C50H36N2S2 (729.0): C, 82.4; H, 4.9; N, 3.8; S, 8.8.
Found: C, 81.9; H, 5.1; N, 3.8; S, 8.4.
2-(N,N-Diarylamino)thiophenes 27; General Procedure
Equivalent amounts of a thioacetamide 21 (0.01 mol) and a bro-
moketone 13 (0.01 mol, 2.0 g) in EtOH (100 mL) were refluxed for
8 h. After cooling the mixture was diluted with ice-water (300 mL)
and the precipitated product was isolated by filtration or, when ob-
tained as oil, titruated with EtOH (20 mL) and recrystallized from
EtOH. The following products were obtained:
N,N -Diphenyl-N,N -bis(3,4,5-triphenyl-2-thienyl)phenylene-
1,4-diamine (40b)
By analogy to the previous procedure N,N -diphenyl-N,N -bis(phe-
nylthioacetyl)phenylene-1,4-diamine (36, 0.01 mol, 5.28 g) and 2-
bromo-1,2-diphenylethanone (13b, 0.02 mol, 5.5 g) in acetic anhy-
dride (100 mL) was stirred for 10 h at 100 °C. After cooling, the
mixture was poured into ice-water (250 mL) and stirred for 4 h. The
precipitate formed was isolated by filtration and recrystallizied
from DMF. The product was obtained in a yield of 5.7 g (65%).
N,N,3,4-Tetraphenyl-2-aminothiophene (27a)
From N,N,2-triphenylacetamide (21a) and phenacylbromide (13a)
in a yield of 2.7 g (67%).
Mp 317 °C.
Mp 102 °C.
Anal. Calcd for C62H44N2S2 (881.2): C, 84.5; H, 5.0; N, 3.2; S, 7.3.
Found: C, 84.7; H, 5.2; N, 2.7; S, 7.4.
Anal. Calcd for C28H21NS (403.5): C, 83.4; H, 5.2; N, 3.5; S, 7.9.
Found: C, 83.4; H, 5.8; N, 3.2; S, 8.2.
N,N -Diphenyl-N,N -bis(3,4-diphenyl-2-thienyl)benzidine (41a)
A mixture of N,N -diphenyl-N,N -bis(phenylthioacetyl)benzidine
(37, 0.01 mol, 6.04 g) and phenacylbromide (13a, 0.02 mol, 4.0 g)
in DMF (100 mL) was stirred for 10 h at 100 °C. After cooling, the
mixture was diluted with ice-water (250 mL). The precipitate
formed was isolated by filtration and recrystallized from DMF. The
product was obtained in a yield of 4.4 g (55%).
N,N,3,4,5-Pentaphenyl-2-aminothiophene (27b)
From N,N,2-triphenylacetamide (21a) and 2-bromo-1,2-diphenyle-
thanone (13b) in a yield of 3.2 g (67%).
Mp 120 °C.
Anal. Calcd for C34H25NS (479.5): C, 85.1; H, 5.2; N, 2.9; S, 6.7.
Found: C, 85.2; H, 5.0; N, 3.0; S, 6.8.
Mp 183 185 °C.
N-(1-Naphthyl)-N,3,4-triphenyl-2-aminothiophene (27c)
From N-(1-naphthyl)-N,2-diphenyl-acetamide (21b) and phenacyl-
bromide (13a) in a yield of 2.3 g (51%).
Anal. Calcd for C56H40N2S2 (805.0): C, 83.6; H, 5.0; N, 3.5; S, 8.0.
Found: C, 82.9; H, 5.2; N, 3.1; S, 7.9.
N,N -Diphenyl-N,N -bis[(3,4,5-triphenyl-2-thienyl]benzidine
(41b)
Mp 64 °C.
Anal. Calcd for C32H23NS (453.6): C, 84.8; H, 5.1; N, 3.1; S, 7.1.
Found: C, 83.6; H, 5.3; N, 3.0; S, 7.5.
In analogy to the previous procedure N,N -diphenyl-N,N -bis(phe-
nylthioacetyl)benzidine (37, 0.01 mol, 6.04 g) and 2-bromo-1,2-
diphenylethanone (13b, 0.02 mol, 5.5 g) in acetic anhydride (100
mL) was stirred for 10 h at 100 °C. After cooling, the mixture was
poured into ice-water (250 mL) and stirred for 4 h. The precipitate
formed was isolated by filtration and recrystallized from DMF. The
product was obtained in a yield of 6.8 g (71%).
N-(2-Naphthyl)-N,3,4,5-tetraphenyl-2-aminothiophene (27d)
From N-(1-naphthyl)-N,2-diphenyl-acetamide (21b) and 2-bromo-
1,2-diphenylethanone (13b) in a yield of 1.2 g (25%).
Mp 198 °C.
Mp 276 °C.
Anal. Calcd for C38H27NS (529.7): C, 86.2; H, 5.1; N, 2.6; S, 6.1.
Found: C, 86.28; H, 5.4; N, 2.3; S, 6.0.
Anal. Calcd for C40H32N2S2 (957.3): C, 85.4; H, 5.0; N, 2.9; S, 6.7.
Found: C, 84.6; H, 5.2; N, 2.8; S, 6.8.
N,N -Diphenyl-N,N -bis(4,5-diphenyl-2-thiazolyl)phenylene-
1,4-diamine (38)
A mixture of N,N -diphenyl-N,N -bis(thiocarbamido)phenylene-
1,4-diamine (34, 0.01 mol, 3.78 g) and 2-bromo-1,2-diphenyletha-
none (13b, 0.02 mol, 5.5 g) in DMF (100 mL) was stirred for 8 h at
100 °C. After cooling, the mixture was diluted with ice-water (250
mL) and the precipitate formed was isolated by filtration, followed
by recrystallization from DMF. The product was obtained in a yield
of 3.9 g (53%).
Acknowledgement
The authors are grateful to the Bundesministerium für Bildung und
Forschung (BMBF) for financial support and to Dr. D. Rohde for re-
cording the thermal and electrochemical data.
References
Mp 302 °C.
(1) Shirota, Y. SPIE 1990, 3148, 186; and references given
Anal. Calcd for C48H34N4S2 (730.9): C, 78.9; H, 4.7; N, 7.7; S, 8.8.
Found: C, 78.9; H, 5.0; N, 7.5; S, 8.3.
therein.
(2) Koene, B. E.; Loy, D. E.; Thompson, M. E. Chem. Mater.
1998, 10, 2235.
Synthesis 2002, No. 9, 1268–1276 ISSN 0039-7881 © Thieme Stuttgart · New York

1276
J. Schumann et al.
PAPER
(3) Pai, D. M.; Yanus, J. F.; Stolka, M. J. Phys. Chem. 1984, 88,
4714.
(10) (a) Thayumanavan, S.; Barlow, S.; Marder, S. R. Chem. Mat.
1997, 9, 3231. (b) Koene, B. E.; Loy, D. E.; Thompson, M.
E. Chem. Mat. 1998, 10, 2235. (c) Bushby, R. J.; Gooding,
D.; Vale, M. E. Philos. Trans. R. Soc. London, Ser. A 1999,
357, 2939. (d) Yamamoto, T.; Nishiyama, M.; Koie, Y.
Teterahedron Lett. 1998, 39, 2367. (e) Yamamoto, T.;
Nishiyama, M.; Koie, Y. Toso Kankyu Hokoku 1997, 41, 49;
Chem. Abstr. 1998, 128, 180. (f) Hartwig, J. F.; Goodson, F.
E.; Luie, J.; Hauck, S. Polym. Mater. Sci. Eng. 1999, 80, 41.
(g) Louie, J.; Hartwig, J. F.; Frey, A. J. Am. Chem. Soc.
1997, 119, 11695.
(4) (a) Rothberg, L. J.; Lovinger, A. J. J. Mater. Res. 1996, 11,
3174. (b) Jüstel, T.; Nikol, H.; Ronda, C. Angew. Chem., Int.
Ed. 1998, 37, 3084; Angew. Chem. 1998, 110, 3250.
(5) (a) Garnier, F.; Hajlaoui, R.; Yassar, A.; Srivastava, P.
Science 1994, 265, 1684. (b) Brown, A. R.; Jarrett, C. P.; de
Leeuw, D. M.; Matters, M. Synth. Met. 1997, 88, 37.
(c) Horowitz, G. Adv. Mat. 1998, 10, 365.
(6) (a) Cariciftci, N. S.; Smilowitz, L.; Heeger, A. J.; Wudl, F.
Science 1992, 258, 1474. (b) Halls, J. J. M.; Walsh, C. A.;
Greenham, N. C.; Marseglia, E. A.; Friend, R. H.; Moratti,
S. C.; Holmes, A. B. Nature 1995, 376, 498.
(11) Watanabe, M.; Yamamoto, T.; Nishiyama, M. Chem.
Commun. 2000, 133.
(7) Getautis, V.; Stanisauskaité, A.; Paliulis, ; Uss, S.; Uss, V. J.
Prakt. Chem. 2000, 342, 58.
(12) (a) Wong, K.-T.; Hung, T. H.; Kao, S. C.; Chou, C. H.; Su,
Y. O. Chem. Commun. 2001, 1628. (b) Gerstner, P.;
Hartmann, H.; Kanitz, A.; Rogler, W. patent submitted.
(13) Becker, H. G. O. In Organikum, 19th ed.; Johann
Ambrosius Barth: Leipzig, 1993.
(14) (a) Liebscher, J. In Thiazoles, Houben-Weyl, Methoden der
Organischen Chemie, Vol. E8b; Georg Thieme: Stuttgart,
1994, 1–398. (b) Wiley, R. H.; England, D. C.; Behr, L. C.
In The preparation of thiazoles, Organic Reactions, Vol. 6;
: , 1951, 367.
(15) Hartmann, H.; Mayer, R. Z. Chem. 1966, 6, 28.
(16) (a) 1-Naphdata: N,N ,N -tris(1-naphthyl)-1,3,5-
trianilinoben-zene, see: Shirota, Y. SPIE 1990, 186, 3148.
(b) -NPD: N,N -bis(1-naphtyl)-N,N -diphenylbenzidine,
see: Koene, B. E.; Loy, D. E.; Thompson, M. E. Chem.
Mater. 1998, 10, 2235.
(17) Kanitz, A.; Schumann, J.; Scheffel, M.; Rajoelson, S.;
Rogler, W.; Hartmann, H.; Rohde, D. Chem. Lett. 2002, in
press.
(8) Ueta, E.; Nakano, H.; Shirota, Y. Chem. Lett. 1994, 2397.
(9) (a) Goodbrand, H. B.; Hu, N. X. J. Org. Chem. 1999, 64,
670 . (b) Abu-abdoun, I. I.; Ledwith, A. Pure Appl. Chem.
1998, A35, 673. (c) Tanaka, H.; Tokito, S.; Okada, A. Chem.
Commun. 1996, 2175. (d) Selby, T. D.; Blackstock, S. C. J.
Am. Chem. Soc. 1998, 120, 12155. (e) Stickley, K. S.;
Blackstock, S. C. Mol. Cryst. Liq. Cryst. Sci. Technol. 1995,
272, 81. (f) Stickley, K. S.; Blackstock, S. C. Tetrahedron
Lett. 1995, 36, 1585. (g) Ishikawa, W.; Inada, H.; Nakomo,
H.; Shirota, Y. Macromol. Symp. 1997, 125, 171.
(h) Thelakkat, M.; Bacher, A.; Fink, R.; Haubner, F.;
Schmidt, H. W. Polym. Prepr. 1997, 38, 396. (i) Thelakkat,
M.; Schmidt, H. W. Adv. Mater. 1998, 10, 219.
(j) Thelakkat, M.; Schulz, C.; Hohle, C.; Strohriegl, P.;
Schmidt, H. W.; Hofmann, U.; Schloter, S.; Haarer, J. Phys.
Chem. Chem. Phys. 1999, 1, 1693. (k) Kamiyama, T.;
Yasuda, Y.; Shirota, Y. Polym. J. 1999, 31, 1165. (l) Inada,
N.; Shirota, Y. J. Mater. Sci. 1993, 3, 219.
(18) Lutz, R. E. J. Am. Chem. Soc. 1927, 49, 1106.
(19) Ruggli, P.; Gassenmeier, E. Helv. Chim. Acta 1939, 22, 496.
(20) Hausknecht, G. Ber. Dtsch. Chem. Ges. 1889, 22, 324.
(21) Neville, R. G.; McGee, J. J. Can. J. Chem. 1963, 41, 2123.
(22) Chem. Abstr. 1994, 120, 137108.
Synthesis 2002, No. 9, 1268–1276 ISSN 0039-7881 © Thieme Stuttgart · New York